Ion exchange resins have been used for retrieving radiocaesium from aqueous waste streams since the earliest days of the nuclear power industry. The physical and chemical properties of Lewatit DN ion exchange resins encapsulated in silica fume (SF)-blended cement were investigated with the aim of producing a stable solid wasteform for possible future disposal in an underground repository. Expansive reactions involving resin swelling in the high pH pore fluid and Ca(OH)2 formation around the resin particles can be suppressed by the addition of 50-75% SF at w/c ratios of 1.400-1.71. The basis of this suppression is the pozzolanic reaction between Ca(OH)2 and SF which consumes Ca(OH)2 and lowers the pH of the pore fluid to less than 10. The total heat evolution of blended cements is similar to that of a neat Portland cement, demonstrating the exothermic nature of the pozzolanic reaction. The use of high w/c ratios in cements containing 50% SF increases the permeability of the matrix. Porosity measurements indicate that this is due to the high free water content of the paste and the relatively high porosity of SF agglomerates. Elevated curing temperatures (up to 85oC) also increase the permeability as a result of coarsening of the microstructure. Despite the inferior physical immobilisation of caesium in high SF-content cements, leach tests, sorption measurements and pore fluid analysis show that chemical retention of caesium is enhanced by blending, more so in blends containing a permanent excess of SF, due to the formation of highly sorptive silica gel and low ratio C-S-H (Ca/Si as low as 0.80). On the other hand, SF-blended cements are more susceptible to physiochemical degradation in simulated groundwater's containing MgSO4. Chemical attack by MgSO4 converts C-S-H gel and silica gel to a non-cementitious magnesium silicate hydrate (identified as sepiolite) in 50-75% SF pastes, resulting in extensive deterioration of the attacked zone.